Effect of EDTA Complexation on the Kinetics and Thermodynamics of Uranium Redox Reactions Catalyzed by Pyrite: A Combined Electrochemical and Quantum-Mechanical Approach

Abstract

Ethylenediaminetetraacetic acid (EDTA), a strong complexing agent, is a common constituent of liquid nuclear waste streams. The interaction of EDTA or other organic or inorganic ligands with uranyl enhances the mobilization of uranium and therefore significantly influences the disposal and remediation of uranium waste. Although numerous studies have focused on the effect of EDTA on the mobilization of environmental uranium, including the adsorption and redox reactions of uranium on mineral surfaces, few studies have differentiated the reaction-controlling steps (diffusion, adsorption, and chemical reaction/electron transfer) occurring at heterogeneous interfaces to assess the effect of EDTA complexation on each of these processes. Here, a combination of in situ electrochemical methods and quantum-mechanical calculations was used to study the effect of EDTA complexation on the kinetics and thermodynamics of redox reactions of uranium at the pyrite-solution interface. Experiments indicate a potential shift of U(VI)/U(V) on the pyrite surface of ∼0.04 V due to surface adsorption and −0.21 V due to EDTA complexation, with similar results from the calculations. The oxidation of the U(IV) reaction is more sensitive to EDTA complexation in solution than that of U(V). Disproportionation, affecting 2/3 of the intermediate pentavalent state, is the rate-limiting step of the overall redox cycle of uranyl. The charge transfer was controlled by diffusion and adsorption processes. EDTA can promote the delivery of free uranyl from the bulk solution to the pyrite–water interface where the reaction takes place, making the electron-transfer process less diffusion-limited. Adsorption of uranyl onto pyrite surfaces in the gradient electric field is multimolecular layer adsorption, through which electron transfer can occur.